CN112490452B - Fuel cell anode catalyst and preparation method and application thereof - Google Patents
Fuel cell anode catalyst and preparation method and application thereof Download PDFInfo
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- CN112490452B CN112490452B CN202011349327.1A CN202011349327A CN112490452B CN 112490452 B CN112490452 B CN 112490452B CN 202011349327 A CN202011349327 A CN 202011349327A CN 112490452 B CN112490452 B CN 112490452B
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method of a fuel cell anode catalyst, which comprises the following steps: mixing carbon powder and titanium nitride powder and sintering to obtain a sintered product; mixing the sintering product with a platinum precursor, ethylene glycol and a pH regulator to obtain a suspension; carrying out microwave chemical reaction on the suspension to obtain a reaction product; and drying and sintering the reaction product to obtain the fuel cell anode catalyst. The invention takes carbon nitride and titanium carbide as carriers to prepare the nitrogen-doped platinum-based catalyst, the catalyst is used for a high-temperature proton exchange membrane fuel cell in the field of electrocatalysis, the catalyst has sulfide poisoning resistance, and the anode of the cell can tolerate the hydrogen sulfide impurity containing ppm level.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a fuel cell anode catalyst, and a preparation method and application thereof.
Background
Electrocatalysts are an important part of fuel cells, where the demand is large. The fuel cell catalyst is easily poisoned by substances such as carbon monoxide and sulfur, and the requirement on the purity of the hydrogen fuel increases the use cost of the fuel cell. Transition metals such as ruthenium, tin, gold, iron and the like are used as anti-poisoning components in the prior art, so that the anti-poisoning performance of platinum on methanol and carbon monoxide is improved; however, fuel cell catalysts have yet to be further improved in terms of high temperature sulfur toxicity resistance.
Disclosure of Invention
In view of the above, the present invention provides a fuel cell anode catalyst, and a preparation method and an application thereof.
The invention provides a preparation method of a fuel cell anode catalyst, which comprises the following steps:
mixing carbon powder and titanium nitride powder and sintering to obtain a sintered product;
mixing the sintering product with a platinum precursor, ethylene glycol and a pH regulator to obtain a suspension;
carrying out microwave chemical reaction on the suspension to obtain a reaction product;
and drying and sintering the reaction product to obtain the fuel cell anode catalyst.
Preferably, the sintering atmosphere of the mixed carbon powder and titanium nitride powder is nitrogen-ammonia atmosphere.
Preferably, the sintering temperature is 600-900 ℃ when the carbon powder and the titanium nitride powder are mixed and sintered.
Preferably, the platinum precursor is selected from one or more of chloroplatinic acid, sodium chloroplatinate and potassium chloroplatinate.
Preferably, the atmosphere for sintering when the reaction product is dried and sintered is a nitrogen-hydrogen atmosphere.
Preferably, the sintering temperature of the reaction product during drying and sintering is 300-800 ℃.
Preferably, the mass ratio of the carbon powder to the titanium nitride powder is (100-200): (100-400).
Preferably, the mass ratio of the carbon powder to the platinum in the platinum precursor is (100-200): 200.
the invention provides a fuel cell anode catalyst prepared by the method in the technical scheme.
The invention provides an application of the fuel cell anode catalyst in the technical scheme in a fuel cell.
The anode catalyst of the fuel cell provided by the invention mainly takes platinum as a main catalytic component and titanium nitride-carbon nitride as an auxiliary catalytic component, and realizes nitrogen doping of the catalyst by ammonia-nitrogen atmosphere treatment and a nitrogen-hydrogen reduction sintering method, so that the anode catalyst has high-temperature sulfur toxicity resistance.
According to the invention, through the nitrogen doping process of the catalyst, the adsorption of poisons is reduced, the sulfur poisoning resistance of the catalyst at high temperature is improved, and the anode activity of the catalyst on sulfur-containing fuel in a high-temperature proton exchange membrane fuel cell is improved. The prepared catalyst is mixed with polybenzimidazole and N-dimethylacetamide and sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As an anode catalyst layer of the high-temperature phosphoric acid fuel cell, high-purity hydrogen and hydrogen containing 10ppm of hydrogen sulfide were used as anode fuels, respectively, and the current density of the anode fuel cell was 200mA/cm compared with that of a fuel cell2The voltage change shows that the catalyst prepared by the invention has excellent sulfur poisoning resistance.
Drawings
FIG. 1 is a transmission electron micrograph of a platinum-titanium nitride-carbon nitride catalyst prepared in example 1 of the present invention at a scale of 20 nm;
FIG. 2 is an X-ray diffraction pattern of a platinum-titanium nitride-carbon nitride catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph showing the anode poisoning polarization of a fuel cell using the Pt-TiN-C catalyst according to example 1 of the present invention;
fig. 4 is a sulfur poisoning resistance electrode test result of the platinum-titanium nitride-carbon nitride catalyst prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The invention provides a preparation method of a fuel cell anode catalyst, which comprises the following steps:
mixing carbon powder and titanium nitride powder and sintering to obtain a sintered product;
mixing the sintering product with a platinum precursor, ethylene glycol and a pH regulator to obtain a suspension;
carrying out microwave chemical reaction on the suspension to obtain a reaction product;
and drying and sintering the reaction product to obtain the fuel cell anode catalyst.
The carbon powder is not particularly limited in the present invention, and carbon support powder for catalyst well known to those skilled in the art may be used, and is preferably conductive carbon powder.
In the invention, the mass ratio of the carbon powder to the titanium nitride powder is preferably (100-200): (100-400), more preferably (100-200): (200-300), most preferably 100: 200.
the mixing method of the carbon powder and the titanium nitride powder is not particularly limited, an ultrasonic mixing rotary evaporation method is preferably adopted, and the ultrasonic dispersion time in the ultrasonic mixing process is preferably 20-30 hours, and more preferably 24 hours. In the present invention, the method for mixing the carbon powder and the titanium nitride powder preferably comprises:
mixing carbon powder and titanium nitride powder in water, ultrasonically dispersing, and then carrying out rotary evaporation and drying.
In the invention, the water is preferably deionized water, the dosage of the water is not particularly limited, and a person skilled in the art can completely dissolve the carbon powder and the titanium nitride powder by adopting a proper dosage of water according to actual conditions; the method of spin-drying is not particularly limited in the present invention, and water may be removed by a spin-drying method well known to those skilled in the art.
In the invention, the carbon powder and the titanium nitride powder are preferably mixed and then ground.
In the invention, the sintering atmosphere of the mixed carbon powder and titanium nitride powder is preferably a nitrogen-ammonia atmosphere; the volume ratio of nitrogen to ammonia in the nitrogen-ammonia atmosphere is preferably 1: (0.5 to 1.5), more preferably 1: 1.
in the invention, the sintering temperature of the mixed carbon powder and titanium nitride powder during sintering is preferably 600-900 ℃, more preferably 650-850 ℃, and most preferably 700-800 ℃; the sintering time of the carbon powder and the titanium nitride powder after mixing is preferably 8-12 hours, and more preferably 10 hours.
In the present invention, the platinum precursor is preferably selected from one or more of chloroplatinic acid, sodium chloroplatinate, and potassium chloroplatinate, and more preferably is chloroplatinic acid.
In the invention, the mass ratio of the carbon powder to the platinum in the platinum precursor is preferably (100-200): 200, more preferably 100: 200.
in the invention, the mass ratio of the ethylene glycol to the platinum in the platinum precursor is preferably (800-1200): 1, more preferably (900-1100): 1, most preferably 1000:1
In the present invention, the pH adjuster is preferably sodium hydroxide.
In the present invention, the pH adjuster is used to adjust the pH of the resulting suspension to preferably 9 to 11, and more preferably 10.
In the present invention, the method of mixing the sintered product with the platinum precursor, ethylene glycol and pH adjuster is preferably ultrasonic dispersion; the time for ultrasonic dispersion is preferably 8-12 hours, and more preferably 10 hours.
In the present invention, the temperature of the microwave chemical reaction is preferably room temperature; the microwave reaction is preferably carried out in a microwave reactor, and the pH value of the microwave reaction is preferably 8-12, more preferably 9-11, and most preferably 10; the microwave reaction time is preferably 1-10 minutes, more preferably 2-8 minutes, and most preferably 3-6 minutes; the power of the microwave reaction is preferably 800-1200W, more preferably 900-1100W, and most preferably 1000W.
In the present invention, the drying preferably further comprises:
and stirring, cleaning and filtering the reaction product.
In the invention, the stirring time is preferably 8-12 hours, and more preferably 10 hours; the cleaning reagent is preferably water, more preferably deionized water, and the resistivity of the deionized water is preferably 18M omega cm. In the invention, in the cleaning and filtering process, preferably, a sodium borohydride aqueous solution is added into the filtrate after the first cleaning and filtering, and the next filtering and cleaning is carried out after no black precipitate appears; after multiple times of filtering and cleaning, adding a silver chloride aqueous solution into the filtrate after final cleaning and filtering, wherein no precipitate is generated, namely the cleaning and filtering are completed; the concentration of the sodium borohydride aqueous solution is preferably 0.01 g/mL; the concentration of the aqueous silver chloride solution is preferably 0.01 g/mL.
In the invention, the drying temperature is preferably 55-65 ℃, and more preferably 60 ℃.
In the present invention, the atmosphere in which the reaction product is sintered when it is dried and sintered is preferably a nitrogen-hydrogen atmosphere; the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen atmosphere is preferably (8-10): 1, more preferably 9: 1.
in the invention, the sintering temperature of the reaction product during drying and sintering is preferably 300-800 ℃, and more preferably 400-600 ℃; the time for drying and sintering the reaction product is preferably 2-3 hours.
In the present invention, after the reaction product is dried and sintered, the method preferably further comprises grinding the obtained sintered product to obtain the fuel cell anode catalyst.
The invention also provides the fuel cell anode catalyst prepared by the method in the technical scheme.
The invention also provides an application of the fuel cell anode catalyst in the technical scheme in a fuel cell, and the fuel cell anode catalyst is preferably used as an anode catalyst layer component of a high-temperature phosphoric acid fuel cell. The invention provides a fuel cell anode catalyst layer, and the preparation method of the fuel cell anode catalyst layer preferably comprises the following steps:
mixing the anode catalyst of the fuel cell with polybenzimidazole and N-N dimethylacetamide to obtain a mixed solution;
and spraying the mixed solution on the surface of porous carbon paper to obtain the anode catalyst layer of the fuel cell.
In the invention, the mass ratio of the fuel cell anode catalyst to the polybenzimidazole and the N-dimethylacetamide is preferably (8-12): 1: (8000-12000), more preferably (9-11): 1: (9000-11000), most preferably 10:1: 10000.
in the invention, the loading amount of the porous carbon paper to the mixed liquid is preferably 0.8-1.2 mgPt/cm2More preferably 1mgPt/cm2。
According to the invention, through the nitrogen doping process of the catalyst, the adsorption of poisons is reduced, the sulfur poisoning resistance of the catalyst at high temperature is improved, and the anode activity of the catalyst on sulfur-containing fuel in a high-temperature proton exchange membrane fuel cell is improved. The prepared catalyst is mixed with polybenzimidazole and N-dimethylacetamide and sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As an anode catalyst layer of the high-temperature phosphoric acid fuel cell, high-purity hydrogen and hydrogen containing 10ppm of hydrogen sulfide were used as anode fuels, respectively, and the current density of the anode fuel cell was 200mA/cm compared with that of a fuel cell2The voltage change shows that the catalyst prepared by the invention has excellent sulfur poisoning resistance.
The starting materials used in the following examples of the present invention are all commercially available products.
Example 1
100mg of active carbon powder which is produced by Cabot (Cabot) company and is named as Vulcan XC-72 in trade name and 200mg of titanium nitride powder are mixed in 100mL of deionized water, and after the mixture is subjected to ultrasonic dispersion for 24 hours, the mixture is subjected to rotary evaporation and drying; sintering the dried powder in a tubular atmosphere furnace, wherein the volume ratio of ammonia to nitrogen in the ammonia-nitrogen atmosphere is 1:1, sintering at 800 ℃ for 10 hours to obtain a sintered product.
Weighing chloroplatinic acid according to the amount of 200mg of platinum, mixing the chloroplatinic acid, the sintered product and a pH regulator (sodium hydroxide) in 100mL of ethylene glycol, and regulating the pH to 10; the mixture was sufficiently ultrasonically dispersed for 10 hours to obtain a suspension.
And placing the suspension in a microwave reactor with the power of 1000W for 5 minutes to obtain a reaction product.
Stirring the reaction product at room temperature for 10 hours, washing and filtering by using deionized water of 18M omega cm, adding 0.01g/mL of sodium borohydride aqueous solution into a first filtrate obtained after filtration, carrying out next filtration when no black precipitate appears in the filtrate, adding 0.01g/mL of silver chloride aqueous solution into a final filtrate after multiple filtration, and carrying out next drying when the filtrate is clear and no white precipitate appears; drying at 60 ℃ to obtain a dried product.
And placing the dried product in a reducing atmosphere furnace for sintering treatment, wherein the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen atmosphere is 1:1, the sintering temperature is 400 ℃, the sintering time is 2 hours, and the obtained sintering product is ground to obtain the platinum-titanium nitride-carbon nitride catalyst.
The platinum-titanium nitride-carbon nitride catalyst prepared in example 1 of the present invention was ultrasonically dispersed in ethanol, and after being drop-coated on a copper mesh and air-dried, the particle size of the catalyst was around 2nm as detected by scanning with a transmission electron microscope, and the result is shown in fig. 1, where the platinum particles are uniformly distributed on the carrier and no aggregation phenomenon occurs.
The platinum-titanium nitride-carbon nitride catalyst prepared in example 1 of the present invention was subjected to X-ray diffraction detection, and the detection result is shown in fig. 2, and it can be seen from fig. 2 that the platinum precursor (chloroplatinic acid) was reduced to platinum particles, and the particle size of the platinum particles was less than 5 nm according to the scherrer equation.
The catalyst prepared in example 1 according to the invention was compared with a commercial platinum-carbon catalyst (Hispec 4000 platinum-carbon catalyst from Johnson Matthey corporation):
respectively ultrasonically cleaning a glassy carbon electrode (diameter is 4mm) by using water, ethanol and 1mol/L sulfuric acid solution, and grinding the electrode to be flat and smooth by using 0.5 mu m and 0.03 mu m of alumina grinding powder; and cleaning and drying the mixture by using the solvent for standby.
5mg of the catalyst prepared in example 1 was dispersed in 1mL of an ethanol solvent containing a Nafion dispersion (containing 5. mu.L of a 5% by mass Nafion dispersion), and the resulting dispersion was ultrasonically dispersed for 20min to obtain a catalyst dispersion ink.
5 mu L of catalyst dispersion ink is dropped on the surface of the glassy carbon electrode, and the glassy carbon electrode is used as a working electrode after being dried for 30min at room temperature. The toxicity resistance of the catalyst was determined using potentiostatic electrolysis: the oxidation current of pure hydrogen gas and the oxidation current of hydrogen sulfide-containing hydrogen gas (hydrogen sulfide content: 10ppm) were compared at a potential of 0.1V (relative to a standard hydrogen electrode), and the results showed that the catalyst prepared in example 1 had a lower decay slope, and the results of the measurements are shown in fig. 3.
The platinum-titanium nitride-carbon nitride catalyst prepared in the example 1 of the invention is mixed with polybenzimidazole and N-dimethylacetamide (mass ratio is 10:1:10000), and the mixture is sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As anode catalyst layer of high temperature phosphoric acid fuel cell; the fuel cell testing method comprises the following steps: an Arbin fuel cell test system is used, the gas flow rate is 500sccm, the fuel gas is not humidified, and the cell working temperature is 180 ℃; high-purity hydrogen and hydrogen containing 10ppm hydrogen sulfide are respectively used as anode fuels, and the current density of a comparative fuel cell is 200mA/cm2The voltage change with time and the detection result are shown in fig. 4, and it can be seen from fig. 4 that the voltage in pure hydrogen is 0.678V, the voltage in hydrogen containing sulfur is 0.671V, and the voltage holding ratio is 98.9%.
Example 2
100mg of active carbon powder which is produced by Cabot (Cabot) company in America and is named as Vulcan XC-72 in trade name and 100mg of titanium nitride powder are mixed in 100mL of deionized water, and after the mixture is subjected to ultrasonic dispersion for 24 hours, the mixture is subjected to rotary evaporation and drying; sintering the dried powder in a tubular atmosphere furnace, wherein the volume ratio of ammonia to nitrogen in the ammonia-nitrogen atmosphere is 1:1, sintering at 800 ℃ for 10 hours to obtain a sintered product.
Weighing chloroplatinic acid according to the amount of 200mg of platinum, mixing the chloroplatinic acid, the sintered product and a pH regulator (sodium hydroxide) in 100mL of ethylene glycol, and regulating the pH to 10; the mixture was sufficiently ultrasonically dispersed for 10 hours to obtain a suspension.
And placing the suspension in a microwave reactor with the power of 1000W for 5 minutes to obtain a reaction product.
Stirring the reaction product at room temperature for 10 hours, and then washing and filtering the reaction product by using deionized water of 18M omega cm; and adding 0.01g/mL of sodium borohydride aqueous solution into the first filtrate obtained after filtration, carrying out next filtration when no black precipitate appears in the filtrate, adding 0.01g/mL of silver chloride aqueous solution into the final filtrate after multiple filtration, carrying out next drying when the filtrate is clear and no white precipitate appears, and drying at 60 ℃ to obtain a dried product.
And (3) placing the dried product in a reducing atmosphere furnace for sintering treatment, wherein the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen atmosphere is 1:1, sintering at 400 ℃ for 2 hours; and grinding the obtained sintered product to obtain the platinum-titanium nitride-carbon nitride catalyst.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 2 of the invention is dispersed in ethanol by ultrasonic wave, and after the platinum-titanium nitride-carbon nitride catalyst is dripped on a copper mesh and dried, the particle size of the catalyst is about 2nm through scanning detection of a transmission electron microscope, platinum particles are uniformly distributed on a carrier, and the aggregation phenomenon is avoided.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 2 of the invention is mixed with polybenzimidazole and N-dimethylacetamide (the mass ratio is 10:1:10000), and the mixture is sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As anode catalyst layer of high temperature phosphoric acid fuel cell; high-purity hydrogen and hydrogen containing 10ppm hydrogen sulfide are respectively used as anode fuels, and the current density of a comparative fuel cell is 200mA/cm2The voltage change (measured by the method in example 1) indicates that the voltage is 0.678V in pure hydrogen, 0.669V in hydrogen containing sulfur, and the voltage holding ratio is 98.6%.
Example 3
200mg of active carbon powder which is produced by Cabot (Cabot) company and is named as Vulcan XC-72 in trade name and 400mg of titanium nitride powder are mixed in 200mL of deionized water, and after the mixture is subjected to ultrasonic dispersion for 24 hours, the mixture is subjected to rotary evaporation and drying; sintering the dried powder in a tubular atmosphere furnace, wherein the volume ratio of ammonia to nitrogen in the ammonia-nitrogen atmosphere is 1:1, sintering at 900 ℃ for 10 hours to obtain a sintered product.
Weighing chloroplatinic acid according to the amount of 200mg of platinum, mixing the chloroplatinic acid, the sintered product and a pH regulator (sodium hydroxide) in 100mL of ethylene glycol, and regulating the pH to 10; the mixture was sufficiently ultrasonically dispersed for 10 hours to obtain a suspension.
And placing the suspension in a microwave reactor with the power of 1000W for 5 minutes to obtain a reaction product.
Stirring the reaction product at room temperature for 10 hours, and then washing and filtering the reaction product by using deionized water of 18M omega cm; adding 0.01g/mL of sodium borohydride aqueous solution into the first filtrate obtained after filtration, carrying out next filtration when no black precipitate appears in the filtrate, adding 0.01g/mL of silver chloride aqueous solution into the final filtrate after multiple filtration, and carrying out next drying when the filtrate is clear and no white precipitate appears; drying at 60 ℃ to obtain a dried product.
And (3) placing the dried product in a reducing atmosphere furnace for sintering treatment, wherein the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen atmosphere is 1:1, sintering at 400 ℃ for 3 hours; and grinding the obtained sintered product to obtain the platinum-titanium nitride-carbon nitride catalyst.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 3 of the invention is dispersed in ethanol by ultrasonic wave, and after the platinum-titanium nitride-carbon nitride catalyst is dripped on a copper mesh and dried, the particle size of the catalyst is about 2nm through scanning detection of a transmission electron microscope, platinum particles are uniformly distributed on a carrier, and the aggregation phenomenon is avoided.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 3 of the invention is mixed with polybenzimidazole and N-dimethylacetamide (the mass ratio is 10:1:10000), and the mixture is sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As anode catalyst layer of high temperature phosphoric acid fuel cell; high-purity hydrogen and hydrogen containing 10ppm hydrogen sulfide are respectively used as anode fuels, and the current density of a comparative fuel cell is 200mA/cm2The voltage change (measured by the method of example 1) indicates that the voltage is 0.678V in pure hydrogen, 0.650V in hydrogen containing sulfur, and the voltage holding ratio is 95.9%.
Example 4
100mg of active carbon powder which is produced by Cabot (Cabot) company in America and is named as Vulcan XC-72 in trade name and 400mg of titanium nitride powder are mixed in 200mL of deionized water, and after the mixture is subjected to ultrasonic dispersion for 24 hours, the mixture is subjected to rotary evaporation and drying; sintering the dried powder in a tubular atmosphere furnace, wherein the volume ratio of ammonia to nitrogen in the ammonia-nitrogen atmosphere is 1:1, sintering at 600 ℃ for 10 hours to obtain a sintered product.
Weighing chloroplatinic acid according to the amount of 200mg of platinum, mixing the chloroplatinic acid, the sintered product and a pH regulator (sodium hydroxide) in 100mL of ethylene glycol, and regulating the pH to 10; the mixture was sufficiently ultrasonically dispersed for 10 hours to obtain a suspension.
And placing the suspension in a microwave reactor with the power of 1000W for 5 minutes to obtain a reaction product.
Stirring the reaction product at room temperature for 10 hours, and then washing and filtering the reaction product by using deionized water of 18M omega cm; adding 0.01g/mL of sodium borohydride aqueous solution into the first filtrate obtained after filtration, carrying out next filtration when no black precipitate appears in the filtrate, adding 0.01g/mL of silver chloride aqueous solution into the final filtrate after multiple filtration, and carrying out next drying when the filtrate is clear and no white precipitate appears; drying at 60 ℃ to obtain a dried product.
And (3) placing the dried product in a reducing atmosphere furnace for sintering treatment, wherein the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen atmosphere is 1:1, sintering at 400 ℃ for 3 hours; and grinding the obtained sintered product to obtain the platinum-titanium nitride-carbon nitride catalyst.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 4 of the invention is dispersed in ethanol by ultrasonic wave, and after the platinum-titanium nitride-carbon nitride catalyst is dripped on a copper mesh and dried, the particle size of the catalyst is about 2nm through scanning detection of a transmission electron microscope, platinum particles are uniformly distributed on a carrier, and the aggregation phenomenon is avoided.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 4 of the invention is mixed with polybenzimidazole and N-dimethylacetamide (the mass ratio is 10:1:10000), and the mixture is sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As anode catalyst layer of high temperature phosphoric acid fuel cell; high-purity hydrogen and hydrogen containing 10ppm hydrogen sulfide are respectively used as anode fuels, and the current density of a comparative fuel cell is 200mA/cm2The voltage change (measured by the method of example 1) indicates that the voltage in pure hydrogen is 0.678V, the voltage in hydrogen containing sulfur is 0.655V, and the voltage holding ratio is 96.6%.
Example 5
200mg of active carbon powder which is produced by Cabot (Cabot) company and is named as Vulcan XC-72 in trade name and 100mg of titanium nitride powder are mixed in 150mL of deionized water, and the mixture is subjected to ultrasonic dispersion for 24 hours and then rotary evaporation and drying; sintering the dried powder in a tubular atmosphere furnace, wherein the volume ratio of ammonia to nitrogen in the ammonia-nitrogen atmosphere is 1:1, sintering at 900 ℃ for 10 hours to obtain a sintered product.
Weighing chloroplatinic acid according to the amount of 200mg of platinum, mixing the chloroplatinic acid, the sintered product and a pH regulator (sodium hydroxide) in 100mL of ethylene glycol, and regulating the pH to 10; the mixture was sufficiently ultrasonically dispersed for 10 hours to obtain a suspension.
And placing the suspension in a microwave reactor with the power of 1000W for 5 minutes to obtain a reaction product.
Stirring the reaction product at room temperature for 10 hours, and then washing and filtering the reaction product by using deionized water of 18M omega cm; adding 0.01g/mL of sodium borohydride aqueous solution into the first filtrate obtained after filtration, carrying out next filtration when no black precipitate appears in the filtrate, adding 0.01g/mL of silver chloride aqueous solution into the final filtrate after multiple filtration, and carrying out next drying when the filtrate is clear and no white precipitate appears; drying at 60 ℃ to obtain a dried product.
And (3) placing the dried product in a reducing atmosphere furnace for sintering treatment, wherein the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen atmosphere is 1:1, sintering at 400 ℃ for 3 hours; and grinding the obtained sintered product to obtain the platinum-titanium nitride-carbon nitride catalyst.
The platinum-titanium nitride-carbon nitride catalyst prepared in the embodiment 5 of the invention is dispersed in ethanol by ultrasonic wave, and after the platinum-titanium nitride-carbon nitride catalyst is dripped on a copper mesh and dried, the particle size of the catalyst is about 2nm through scanning detection of a transmission electron microscope, platinum particles are uniformly distributed on a carrier, and the aggregation phenomenon is avoided.
The platinum-titanium nitride-carbon nitride catalyst prepared in the example 5 of the invention is mixed with polybenzimidazole and N-dimethylacetamide (the mass ratio is 10:1:10000), and the mixture is sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As anode catalyst layer of high temperature phosphoric acid fuel cell; high-purity hydrogen and hydrogen containing 10ppm hydrogen sulfide are respectively used as anode fuels,comparative fuel cell at a current density of 200mA/cm2Voltage change (detected as in example 1); the results showed that the voltage was 0.678V in pure hydrogen, 0.662V in hydrogen containing sulfur, and the voltage holding ratio was 97.6%.
The anode catalyst of the fuel cell provided by the invention mainly takes platinum as a main catalytic component and titanium nitride-carbon nitride as an auxiliary catalytic component, and realizes nitrogen doping of the catalyst by ammonia-nitrogen atmosphere treatment and a nitrogen-hydrogen reduction sintering method, so that the anode catalyst has high-temperature sulfur toxicity resistance. According to the invention, through the nitrogen doping process of the catalyst, the adsorption of poisons is reduced, the sulfur poisoning resistance of the catalyst at high temperature is improved, and the anode activity of the catalyst on sulfur-containing fuel in a high-temperature proton exchange membrane fuel cell is improved. The prepared catalyst is mixed with polybenzimidazole and N-dimethylacetamide and sprayed on the surface of porous carbon paper, and the loading capacity is 1mgPt/cm2As an anode catalyst layer of the high-temperature phosphoric acid fuel cell, high-purity hydrogen and hydrogen containing 10ppm of hydrogen sulfide were used as anode fuels, respectively, and the current density of the anode fuel cell was 200mA/cm compared with that of a fuel cell2The voltage change shows that the catalyst prepared by the invention has excellent sulfur poisoning resistance.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (8)
1. A method of preparing a fuel cell anode catalyst comprising:
mixing carbon powder and titanium nitride powder and sintering to obtain a sintered product;
mixing the sintering product with a platinum precursor, ethylene glycol and a pH regulator to obtain a suspension;
carrying out microwave chemical reaction on the suspension to obtain a reaction product;
drying and sintering the reaction product to obtain the fuel cell anode catalyst; the sintering atmosphere is nitrogen-ammonia atmosphere when the carbon powder and the titanium nitride powder are mixed and sintered;
the atmosphere of sintering when the reaction product is dried and sintered is a nitrogen-hydrogen atmosphere.
2. The method as claimed in claim 1, wherein the sintering temperature of the carbon powder and the titanium nitride powder is 600-900 ℃ after mixing.
3. The method of claim 1, wherein the platinum precursor is selected from one or more of chloroplatinic acid, sodium chloroplatinate, and potassium chloroplatinate.
4. The method according to claim 1, wherein the temperature of the reaction product during drying and sintering is 300 to 800 ℃.
5. The method according to claim 1, wherein the mass ratio of the carbon powder to the titanium nitride powder is (100-200): (100-400).
6. The method according to claim 1, wherein the mass ratio of the carbon powder to the platinum in the platinum precursor is (100-200): 200.
7. a fuel cell anode catalyst prepared according to the method of claim 1.
8. Use of the fuel cell anode catalyst of claim 7 in a fuel cell.
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